EP0544840A1 - Monomeric recovery from polymeric materials. - Google Patents
Monomeric recovery from polymeric materials.Info
- Publication number
- EP0544840A1 EP0544840A1 EP91920743A EP91920743A EP0544840A1 EP 0544840 A1 EP0544840 A1 EP 0544840A1 EP 91920743 A EP91920743 A EP 91920743A EP 91920743 A EP91920743 A EP 91920743A EP 0544840 A1 EP0544840 A1 EP 0544840A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymeric material
- recovery
- monomeric component
- material according
- monomeric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B49/00—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
- C10B49/16—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with moving solid heat-carriers in divided form
- C10B49/20—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with moving solid heat-carriers in divided form in dispersed form
- C10B49/22—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with moving solid heat-carriers in divided form in dispersed form according to the "fluidised bed" technique
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
Definitions
- This invention relates generally to a process for recovering monomers from polymers by pyrolysis. More particularly, the process is characterized by high heating rates and short residence times.
- Plastics account for about 7% by weight of municipal solid waste and a larger percentage, 14-21%, by volume according to an Environmental Protection Agency report to Congress, "Methods to Manage and Control Plastic Wastes.” The report predicts that plastic wastes will increase 50% by weight by the year 2000.
- Incineration, landfilling, source reduction and recycling are currently viewed as the main solutions to this mounting problem.
- the main focus is on recycling through grinding separated wastes and re-melting or re-processing.
- Such materials in general, are limited in use to low quality plastics such as decorative (non-load bearing) artificial lumber or are used in small amounts as filler in other plastics. Even these applications require relatively uniform polymer compositions that can only be achieved by expensive presorting of materials.
- some preliminary work has begun on the conversion of plastics to fuels.
- 660-672 have investigated the pyrolysis of waste plastic in a fluidized bed of sand.
- Polyethylene was found to yield 33.8 and 44.7 wt% ethylene at 740 and 840 °C, respectively.
- the carbon residue increased from 0.4 to 1.4 wt% with increasing temperature.
- Aromatic compounds increased from 0.2 to 8.4 wt% with increasing temperature while aliphatic compounds with more than 4 carbons decreased from 4.6 to 1.5 wt%.
- Gaseous hydrocarbons of 4 or fewer carbons and hydrogen increased from 0.4 to 0.9 wt%.
- Polyvinylchloride yielded 56.3 and 56.4 wt% HCl at 740 and 845 °C, respectively.
- Hydrocarbons with 4 or fewer carbons and hydrogen decreased from 6.4 to 5.8 wt% while aromatics increased from 10.9 to 11.5 wt%.
- Polypropylene yielded 13.9 wt% ethylene, 13.7 wt% propylene, 57.3 wt% hydrocarbons with 4 or less carbons, 19.5 wt% hydrocarbons with more than 4 carbons and 19.8 wt% aromatics at 740 °C.
- a 7:2:2:1 by weight mixture of polyethylene: polyvinylchloride:polystyrene:polypropylene gave 13.2 wt% ethylene, 2.7 wt% propylene, 10.5 wt% styrene, 8.1 wt% HCl, 33.5 wt% hydrocarbons with 4 or less carbons and hydrogen, 3.1 wt% hydrocarbons with more than 4 carbons and 36.7 wt% aromatics.
- the general objective or these studies was to obtain a high level of aromatics to be used as chemical raw materials and that longer residence times contributed to an increase in aromatics such as toluene and benzene.
- the present invention solves the prior art waste polymer disposal problem by providing a plastic recovery process that converts mixed plastic wastes into monomer feedstock with minimal, if any, amounts of solid carbon (char) and non-monomeric liquid products.
- the primary product from the process is ethylene based on the composition of typical polymeric plastic wastes.
- a product gas containing about 50 volume percent ethylene has been produced from a mixed polymer feedstock.
- the product gas can be fed to an ethylene purification plant to produce the high purity feedstock for polymerization or other uses using known technology.
- the process treats coarsely ground plastic scrap without presorting at high throughputs (over 1000 lb/hr ft 2 of reactor area) to yield the desired products at low cost.
- waste plastics can be converted into high value virgin feed material rather than the current low value filler-type products.
- the high conversion levels achieved along with the compact size of the equipment provide favorable process economics.
- Preliminary estimates using a mixed plastic feedstock showed that ethylene can be produced for about $0,015 per pound. These costs include all non-feedstock operating and capital related costs for a 500 ton/day recovery plant.
- the process of this invention converts polymeric materials to monomeric components by heating the polymeric materials to a temperature of about 650 to about 1000 °C in less than about 2 sec. Such pyrolysis temperatures are achieved by heating the polymeric materials at a rate between about 500 to about 50,000 °C per sec at atmospheric pressure. Higher heating rates allow for a reduction in heating time to less than about 0.5 sec or even less than about 0.02 sec.
- the process uses a circulating, fluidized-bed reactor (CFB) as the pyrolysis unit to rapidly heat the polymers while preventing recombination to polymer or other undesired by-products.
- Heat is supplied to the CFB by a stream of hot sand or other heat transfer materials.
- the sand is heated in a separate combustor using waste gas, fuel gas, coal, oil, natural gas, or other fuel as the heat source. Contaminants present in these materials remain in the circulating phase or exit with the flue gas from the combustor.
- the short residence times of less than 2 seconds in the CFB coupled with the extremely high heat up rates caused by incandescent sand particles contacting the plastic particles result in pyrolysis of the plastic without recombination or cracking.
- Pyrolysis takes place in the range of about 650 °C to about 1000 °C and at atmospheric pressure.
- the preferred pyrolysis temperature is about 800 °c to about 900 ⁇ C.
- 50,000 °C/sec are achieved by initially heating the fluidized bed and heat transfer material in a combustor to a temperature about 100-200 ⁇ C higher than the desired operating temperature of the pyrolysis unit.
- the heated fluidized bed and heat transfer material is passed into the pyrolysis unit along with a transport gas.
- Polymeric material is fed to the pyrolyzer by means of a screw or other feeder at a rate of more than about 500 lb/hr ft 2 in a manner so as to achieve cocurrent flow.
- the polymeric material breaks down to monomer and is removed from the reactor in less than about 2 seconds.
- the heat transfer material is separated by means of a cyclone or other physical separation device and returned to the combustor for reheating.
- the ratio of fluidized bed heat-transfer and reactor material to polymeric feed material can be 1-100:1 but preferably about 20:1 wt/wt for the above combustor and CFB temperature differences.
- the ratio of heat transfer material to feed material varies with the temperature difference between the CFB and combustor.
- the ratio can be as high as about 100:1 or as low as about 1:1.
- the CFB heat-transfer material also serves as the CFB circulating fluidized bed.
- the fluidized-bed heat transfer and reactor bed material can be any suitable material capable of withstanding the combustor and CFB temperatures.
- refractory materials such as silica, alumina or zirconia or refractory material mixtures are used.
- the fluidized bed and heat-transfer material is a silica sand.
- Various catalytically-active materials may be used in the CFB, either alone or with other bed materials, to enhance the pyrolysis reaction or otherwise influence the product yield or composition.
- Such materials include, but are not limited to, zeolites and various metal catalysts including transition metals such as platinum or iron.
- CFB chemically-active materials
- calcium oxide may be added to the fluidized bed to eliminate acid gases such as the HCl formed from the pyrolysis of polyvinyl chloride.
- a non-oxidizing transport gas is used to circulate and fluidize the bed.
- a transport gas may be essentially inert gases such as nitrogen, argon or helium.
- steam is used to improve the yields of monomer.
- Recycle gas from the fluidized bed may also be used as the transport gas.
- polyethylene accounts for about 72% of all packaging materials (31.2% high-density polyethylene (HDPE) ; 30.9% low-density polyethylene (LDPE) ; and 10.3% polyethylene (PE) , with polystyrene (PS) accounting for another 11.2%; polyvinyl chloride (PVC) 5.5% and 11.0% other) .
- HDPE high-density polyethylene
- LDPE low-density polyethylene
- PS polystyrene
- PVC polyvinyl chloride
- LDPE was converted in 50 wt% yield at a temperature of 840 °C.
- ethylene was formed in 59 wt% yield.
- the major remaining products were propylene, butylene, hydrogen and methane.
- PS was converted in about 21% yield at 870 °C.
- styrene and ethylene were formed in 33 and 21% yield, respectively.
- the major remaining products were benzene, methane, hydrogen, toluene, acetylene, ethane, C0 2 , and CO.
- PVC was converted in about a 50 wt% yield at a temperature of 840 °C.
- ethylene was formed in 16 wt% yield. Vinyl chloride monomer was not formed. Chlorine was removed as HCl.
- the major remaining products were hydrogen, propylene, methane, C0 2 , and CO.
- the following products were obtained: ethylene 58.0%, methane 18.6%, propylene 10.0%, butylene 6.2%, benzene 2.6% and styrene 1.9%.
- FIG. 1 is a flow diagram of the circulating fluidized bed pyrolysis unit of this invention.
- FIG. 2 illustrates the total conversion of polyethylene with temperature and the amount of ethylene produced in the converted material.
- Ordinate A shows the carbon conversion to gas.
- Ordinate C shows the fraction converted to monomer. Temperature is shown in °C (abscissa B) .
- FIG. 3. shows the mole fraction of components (ordinate A) in the product gas from the pyrolysis of low- density polyethylene using steam as a transport gas. Temperature is shown in °C (abscissa B) .
- FIG. 4. shows the mole fraction of components (ordinate A) in the product gas from the pyrolysis of low- density polyethylene using nitrogen as a transport gas. Temperature is shown in °C (abscissa B) .
- FIG. 5 illustrates the mole fraction of components (ordinate A) in the product gas from the pyrolysis of high-density polyethylene using steam as a transport gas. Temperature is shown in °C (abscissa B) .
- FIG. 1 is a flow diagram of the circulating fluidized bed (CFB) pyrolyzer system of this invention.
- the CFB pyrolyzer 2 is a 2-inch diameter (5.04 cm) modular unit 10 feet long (305 cm) and made out of stainless steel.
- Heat is supplied to the CFB pyrolyzer by means of a heat transfer material such as silica sand which enters the pyrolyzer at a rate of 5 to 30 lb/lb of polymer feed.
- the heated sand also serves as the fluidized bed material.
- the grain size of the sand is such that is can be entrained from the reactor.
- the sand enters combustor 4, a fluidized-bed combustor, through passage 6. It is heated in combustor 4 using waste gas, fuel gas, coal, oil, natural gas, or other fuel as the heat source.
- the combustor fuel enters the combustor through line 8.
- Air enters the combustor through line 14.
- the sand is heated to a temperature about 100-200 °C higher than the desired operating temperature of the CFB pyrolyzer unit 2. Ash, if any, from the combustion process is withdrawn from combustor 4 through line 20. After the sand is heated, it enters cyclone 12 through line 10 where gaseous contaminants present in the sand, fuel, or air leave with the flue gas from the combustor 4 through line 16.
- sand is preferably used as the heat transfer and CFB reactor material, it is to be understood that other heat-withstanding materials may be substituted for or used along with the sand.
- a wide variety of refractory-type materials are well known and can also be used as the heat transfer material. Such refractory-type materials include materials such as silica, alumina, and zirconia. Silica sand is preferred because of its availability and low cost.
- Catalytically-active materials such as, but not limited to, zeolites and metals such as the transition metals iron and platinum can be used in the CFB to influence the pyrolysis reaction or product yield composition.
- Chemically-active materials may also be used in the CFB to influence or control the reaction or products.
- calcium oxide can be added to eliminate acid gases such as HCl that are formed in the pyrolysis of polyvinyl chloride.
- a non-oxidizing transport gas such as steam is used to fluidize and circulate the bed in the CFB pyrolyzer 2.
- the difference in product yield with the use of steam as a transport gas and nitrogen is illustrated in FIGS. 3 and 4.
- Other transport gases such as argon, helium or recycle gas from the fluidized bed may also be used.
- the transport gas enters the CFB pyrolyzer 2 through line 22.
- the polymeric materials to be fed into the CFB pyrolyzer are coarsely ground to a solid particle size of less than about 1 inch (2.54 cm). Generally, it has been found that the size of the ground material is not a pyrolysis factor but rather a convenient handling size given the size of the pyrolyzer 2 and input line 24.
- the ground material is fed to the CFB pyrolyzer 2 through line 24 in solid form by means of a screw or other feeder at a rate of about 45 kg/hr (1.2kg/hr-cm 2 ) .
- the ground polymeric materials preferably pass through the CFB in cocurrent flow with the fluidized bed material.
- the CFB pyrolyzer heat transfer material e.g., sand
- the ratio of the CFB pyrolyzer heat transfer material, e.g., sand, to the amount of polymer material (feed) in the CFB is about 20:1 wt/wt.
- the ratio can be as high as about 100:1 and as low as about 1:1.
- the ratio of sand to polymeric material is adjusted according to the temperature differences between the CFB 2 and the combustor 4.
- the polymeric material and its gaseous pyrolysis products spend less than about 2 seconds in the CFB. During this time, they are heated to a temperature of between about 650 °C to about 1000 °C. Due to the slip velocity constraints, the sand and some of the solid polymer particles backmix and may reside in the CFB for a somewhat longer period. This longer residence of some polymer particles is not critical to the invention. It is generally known that the time various particles remain in the CFB follows a statistical distribution that is skewed toward longer residence times. Thus it is to be understood that the CFB heating time periods given for polymeric materials in the specification and claims refer specifically to a mean residence time.
- Sand and unreacted polymer reenter the combustor through line 6.
- the gaseous reaction products and steam leave the cyclone 28 through line 30 and enter cooler 32 where the product monomers are separated from the other gaseous products and steam according to known methodology such as that described in the Kirk-Othmer Encyclopedia of Chemical Technology, Interscience Encyclopedia, Inc. 1950, vol. 5, pp. 890-89.
- Product monomers leave the cooler through line 34.
- Example 1 Approximately 300 lbs of silica sand were heated in a 12-inch diameter fluidized bed combustor. The sand was heated to a temperature about 100-200 °C above the desired temperature of a 2-inch diameter, 10-foot long CFB pyrolyzer after which it was allowed to circulate into the CFB using steam as a transport gas. The temperature of the pyrolyzer was adjusted to the operating temperature by adjusting the sand circulation rate. About 100 lbs of low density polyethylene pellets with an average size of about V were fed into the CFB in cocurrent flow by means of a screw at a rate of about 20 lbs/hr. Reaction products from the CFB were feed into a cooler and then onto a gas chromatograph system for analysis.
- Low density polyethylene was subjected to the CFB pyrolysis reaction described in Example 1 except that nitrogen was used as a transport gas rather than steam.
- Example 3 High density polyethylene was subjected to the CFB pyrolysis reaction described in Example l. Results are given in Table III. Carbon monoxide and carbon dioxide were measured at negligible levels.
- Example 4 Polystyrene was subjected to the CFB pyrolysis reaction described in Example 1. Monomer yields and product gas composition are given in Table IV.
- Example 5 Polyvinyl chloride was subjected to the CFB pyrolysis reaction described in Example 1. Results are given in Table V.
- Example 6 A mixed plastic polymer composition representative of a waste mixture of polymeric materials with a plastic distribution of 49.2 wt% LDPE, 34.5 wt% HDPE, 11.3 wt% PS, and 5.0 wt% PVC was subjected to the CFB pyrolysis reaction described in Example 1. Results are given in Table VI.
- Example 1 polypropylene yields ethylene and propylene as the main products.
- a mixture as used in Example 6 and also containing polypropylene yields additional amounts of onomeric propylene.
- Refractory materials such as alumina, silica, or zirconia can be substituted for silica sand.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US571196 | 1984-01-19 | ||
US07/571,196 US5136117A (en) | 1990-08-23 | 1990-08-23 | Monomeric recovery from polymeric materials |
PCT/US1991/005976 WO1992004423A2 (en) | 1990-08-23 | 1991-08-21 | Monomeric recovery from polymeric materials |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0544840A1 true EP0544840A1 (en) | 1993-06-09 |
EP0544840B1 EP0544840B1 (en) | 1995-12-27 |
Family
ID=24282703
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91920743A Expired - Lifetime EP0544840B1 (en) | 1990-08-23 | 1991-08-21 | Ethylene recovery from polymeric materials |
Country Status (8)
Country | Link |
---|---|
US (2) | US5136117A (en) |
EP (1) | EP0544840B1 (en) |
JP (1) | JPH06500592A (en) |
AT (1) | ATE132178T1 (en) |
CA (1) | CA2088585C (en) |
DE (1) | DE69115912T2 (en) |
ES (1) | ES2084192T3 (en) |
WO (1) | WO1992004423A2 (en) |
Cited By (1)
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WO2022038316A1 (en) | 2020-08-20 | 2022-02-24 | Teknologian Tutkimuskeskus Vtt Oy | Method and process arrangement for producing hydrocarbons and use |
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- 1991-08-21 ES ES91920743T patent/ES2084192T3/en not_active Expired - Lifetime
- 1991-08-21 AT AT91920743T patent/ATE132178T1/en not_active IP Right Cessation
- 1991-08-21 JP JP3518529A patent/JPH06500592A/en active Pending
- 1991-08-21 CA CA002088585A patent/CA2088585C/en not_active Expired - Fee Related
- 1991-08-21 EP EP91920743A patent/EP0544840B1/en not_active Expired - Lifetime
- 1991-08-21 WO PCT/US1991/005976 patent/WO1992004423A2/en active IP Right Grant
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WO2022038316A1 (en) | 2020-08-20 | 2022-02-24 | Teknologian Tutkimuskeskus Vtt Oy | Method and process arrangement for producing hydrocarbons and use |
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WO1992004423A3 (en) | 1992-06-25 |
DE69115912T2 (en) | 1996-08-22 |
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CA2088585A1 (en) | 1992-02-24 |
DE69115912D1 (en) | 1996-02-08 |
CA2088585C (en) | 2003-02-04 |
WO1992004423A2 (en) | 1992-03-19 |
JPH06500592A (en) | 1994-01-20 |
US5136117A (en) | 1992-08-04 |
EP0544840B1 (en) | 1995-12-27 |
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